JP2010086657A - Nonaqueous electrolyte secondary battery - Google Patents

Nonaqueous electrolyte secondary battery Download PDF

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JP2010086657A
JP2010086657A JP2008250991A JP2008250991A JP2010086657A JP 2010086657 A JP2010086657 A JP 2010086657A JP 2008250991 A JP2008250991 A JP 2008250991A JP 2008250991 A JP2008250991 A JP 2008250991A JP 2010086657 A JP2010086657 A JP 2010086657A
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positive electrode
secondary battery
lithium
electrolyte secondary
aqueous electrolyte
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Masanori Nakanishi
正典 中西
Hidetoshi Tanaka
秀敏 田中
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FDK Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery equipped with a cathode excellent in such characteristics as electron conductivity and ion conductivity without pulverization, with the use of lithium iron phosphoric acid compound. <P>SOLUTION: The nonaqueous electrolyte secondary is configured such that a cathode (1) with a lithium-content compound and an anode (2) are immersed in nonaqueous electrolyte solution. The lithium-content compound of the cathode is a lithium iron phosphoric acid compound of an olivine type structure expressed in LiFe<SB>1-x</SB>M<SB>x</SB>PO<SB>4</SB>, wherein M is one or more elements selected from Ni, Co, Mn, Mg, Al, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn, Mo, and Y, and is 0<x≤0.99. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

本発明は、特に、リチウムイオン二次電池などの非水電解液二次電池における新規正極材料として注目されているオリビン型構造のリチウム鉄リン酸化合物の性能改良に関するものである。   In particular, the present invention relates to an improvement in the performance of a lithium iron phosphate compound having an olivine structure that is attracting attention as a novel positive electrode material in a non-aqueous electrolyte secondary battery such as a lithium ion secondary battery.

上記リチウムイオン二次電池の正極材料としてＬｉＣｏＯ2やＬｉＮｉＯ2が普及しているものの、これらＬｉＣｏＯ2やＬｉＮｉＯ2は、その結晶構造が層状構造を有して不安定であって、過充電による劣化が生じ、あるいは繰り返しの充放電サイクルにより著しく充電容量が減少するなどの欠点がある。 Although LiCoO 2 and LiNiO 2 are widely used as the positive electrode material of the lithium ion secondary battery, these LiCoO 2 and LiNiO 2 are unstable because their crystal structure has a layered structure, and are deteriorated by overcharge. Or the charge capacity is significantly reduced by repeated charge / discharge cycles.

そこで、近年、特許文献１〜３に示すように、新規正極材料である結晶構造の安定なオリビン型構造のリチウム鉄リン酸化合物が新たな次世代自動車や定置用大型電池などの正極活物質としても注目されている。
このリチウム鉄リン酸化合物は、上述のように結晶構造が安定であるため、過充電による劣化や繰り返しの充放電サイクルによる充放電容量の減少を防ぐことができる。 Therefore, in recent years, as shown in Patent Documents 1 to 3, a lithium ion phosphate compound having a stable olivine structure with a crystal structure, which is a novel positive electrode material, is used as a positive electrode active material for new next-generation automobiles and large stationary batteries. Is also attracting attention.
Since this lithium iron phosphate compound has a stable crystal structure as described above, it is possible to prevent deterioration due to overcharge and reduction in charge / discharge capacity due to repeated charge / discharge cycles.

さらに、このリチウム鉄リン酸化合物は、ＬｉＣｏＯ2やＬｉＮｉＯ2と比較して、ＣｏやＮｉなどの昨今急激な価格の高騰が生じているレアメタルの使用量を減少させることができ、さらには、レアメタルを使用せずに安価なリチウムイオン二次電池の製作も可能になる。 Furthermore, this lithium iron phosphate compound can reduce the amount of rare metals used in recent years, such as Co and Ni, which have experienced rapid price increases, compared to LiCoO 2 and LiNiO 2. This makes it possible to manufacture an inexpensive lithium ion secondary battery without using the battery.

特開２００４−５１４６３９号公報Japanese Patent Application Laid-Open No. 2004-514639 特開２００３−３２３８９２号公報JP 2003-338992 A 特開２００１−１１０４１４号公報JP 2001-110414 A

その一方で、リチウム鉄リン酸化合物は、粒子内でのリチウムイオンによるイオン伝導性や粒子間での電子伝導性が低いことから、次世代自動車などに用いるには所望の出力が得られないという問題がある。   On the other hand, the lithium iron phosphate compound has low ion conductivity due to lithium ions in the particles and electron conductivity between the particles, so that a desired output cannot be obtained for use in next-generation automobiles. There's a problem.

このため、一般的に、リチウム鉄リン酸化合物をナノレベルまで微粒子化して、この微粒子化したリチウム鉄リン酸化合物にカーボンや貴金属などの導電剤を添加、あるいは上記微粒子化したリチウム鉄リン酸化合物の表面に上記導電剤を被覆することにより、電子伝導性の改善を図っている。   For this reason, generally, a lithium iron phosphate compound is made fine to the nano level, and a conductive agent such as carbon or noble metal is added to the finely divided lithium iron phosphate compound, or the above-mentioned finely divided lithium iron phosphate compound The surface of the film is coated with the conductive agent to improve the electron conductivity.

しかしながら、リチウム鉄リン酸化合物は、上記微粒子化により一次粒子の凝集が起こり易くなるため、上記正極を製作する際にスラリー調製が困難となるだけでなく、バインダー使用量が増加して微粒子化したわりに電子伝導性の改善による抵抗減少の効果が得にくい。これに加えて、粒子間の空隙が少なくなるため、繰り返しの充放電サイクルにより電解液が浸透しにくくなり、抵抗上昇および活物質の利用率の低下を引き起こすという問題がある。   However, since the lithium iron phosphate compound tends to cause aggregation of primary particles due to the above-mentioned micronization, not only the slurry preparation becomes difficult when manufacturing the positive electrode, but also the amount of binder used is increased and micronized. Instead, it is difficult to obtain the effect of reducing resistance by improving the electron conductivity. In addition to this, since the voids between the particles are reduced, there is a problem that the electrolytic solution is less likely to permeate through repeated charge / discharge cycles, causing an increase in resistance and a decrease in utilization rate of the active material.

本発明は、かかる事情に鑑みてなされたもので、リチウム鉄リン酸化合物を用いて微粒子化することなく、電子伝導性やイオン伝導性などの特性に優れた正極を備えた非水電解液二次電池を提供することを課題とするものである。   The present invention has been made in view of such circumstances. A non-aqueous electrolyte solution having a positive electrode excellent in characteristics such as electron conductivity and ion conductivity without being atomized using a lithium iron phosphate compound. It is an object to provide a secondary battery.

すなわち、請求項１に記載の発明に係る非水電解液二次電池は、負極と、リチウム含有化合物を備えた正極とが非水電解液に浸漬されてなる非水電解液二次電池において、前記正極のリチウム含有化合物は、ＬｉＦｅ1-xＭxＰＯ4であって、ＭがＬｉ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇ、Ａｌ、Ｔｉ、Ｇａ、Ｃｕ、Ｖ、Ｎｂ、Ｚｒ、Ｃｅ、Ｉｎ、Ｚｎ、ＭｏおよびＹの中から選択される一種以上の元素であり、かつ０＜ｘ≦０．９９のオリビン型構造のリチウム鉄リン酸化合物からなることを特徴としている。 That is, the non-aqueous electrolyte secondary battery according to the invention of claim 1 is a non-aqueous electrolyte secondary battery in which a negative electrode and a positive electrode including a lithium-containing compound are immersed in the non-aqueous electrolyte. The lithium-containing compound of the positive electrode is LiFe 1-x M x PO 4 , where M is Li, Ni, Co, Mn, Mg, Al, Ti, Ga, Cu, V, Nb, Zr, Ce, In, It is one or more elements selected from Zn, Mo and Y, and is characterized by comprising a lithium iron phosphate compound having an olivine structure of 0 <x ≦ 0.99.

請求項２に記載の発明は、請求項１に記載の非水電解液二次電池において、前記正極のリチウム含有化合物は、その平均粒子径が０．１μｍ以上１００μｍ以下であり、かつ粒子表面積が球体とみなした場合の表面積の２０倍以上１００倍以下であることを特徴としている。   The invention according to claim 2 is the nonaqueous electrolyte secondary battery according to claim 1, wherein the lithium-containing compound of the positive electrode has an average particle size of 0.1 μm or more and 100 μm or less and a particle surface area. It is characterized by being 20 times to 100 times the surface area when regarded as a sphere.

請求項３に記載の発明は、請求項１または２に記載の非水電解液二次電池において前記正極のリチウム含有化合物は、その表面が導電剤で被覆されていることを特徴としている。   The invention described in claim 3 is characterized in that in the non-aqueous electrolyte secondary battery according to claim 1 or 2, the surface of the lithium-containing compound of the positive electrode is coated with a conductive agent.

請求項４に記載の発明は、請求項３に記載の非水電解液二次電池において、前記導電剤が炭素であることを特徴としている。   According to a fourth aspect of the present invention, in the nonaqueous electrolyte secondary battery according to the third aspect, the conductive agent is carbon.

請求項５に記載の発明は、請求項３または４に記載の非水電解液二次電池において、前記導電剤が賦活処理により多孔質化されていることを特徴としている。   The invention according to claim 5 is the nonaqueous electrolyte secondary battery according to claim 3 or 4, characterized in that the conductive agent is made porous by activation treatment.

請求項１〜５に記載の非水電解液二次電池によれば、リチウム鉄リン酸化合物として、ＬｉＦｅＰＯ4 のＦｅの一部を上記Ｍに置換したものを用いることによって、すなわち、ＬｉＦｅ1-xＭxＰＯ4のＭがＬｉ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇ、Ａｌ、Ｔｉ、Ｇａ、Ｃｕ、Ｖ、Ｎｂ、Ｚｒ、Ｃｅ、Ｉｎ、Ｚｎ、ＭｏおよびＹの中から選択される一種以上の元素であって、０＜ｘ≦０．９９のものを用いることによって、粒子内のイオン伝導性を著しく向上させることができる。 According to the nonaqueous electrolyte secondary battery according to any one of claims 1 to 5, by using a lithium iron phosphate compound in which a part of Fe in LiFePO 4 is replaced with M, that is, LiFe 1− x M x PO 4 is one or more selected from the group consisting of Li, Ni, Co, Mn, Mg, Al, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn, Mo and Y By using an element of 0 <x ≦ 0.99, the ionic conductivity in the particles can be remarkably improved.

特に、請求項２に記載の非水電解液二次電池によれば、リチウム鉄リン酸化合物の平均粒子径を０．１〜１００μｍとしたため、凝集の発生を抑制して、安定したスラリー調製を行うことができる。これに加えて、リチウム含有化合物の粒子表面積を球体とみなした場合の表面積の２０倍以上１００倍以下、すなわち、ラフネスファクターを２０倍以上１００倍以下としたため、上述の粒子内のイオン伝導性を一段と向上させることができ、上述のように微粒子化しなくとも、リチウム含有化合物の粒子内部まで電池反応を行わせることが可能となる。   In particular, according to the non-aqueous electrolyte secondary battery according to claim 2, since the average particle diameter of the lithium iron phosphate compound is 0.1 to 100 μm, the occurrence of aggregation is suppressed and stable slurry preparation is achieved. It can be carried out. In addition to this, since the particle surface area of the lithium-containing compound is 20 times to 100 times the surface area when regarded as a sphere, that is, the roughness factor is 20 times to 100 times, the ionic conductivity in the particles described above is increased. The battery reaction can be carried out even inside the lithium-containing compound particles without making fine particles as described above.

請求項３に記載の非水電解液二次電池によれば、リチウム含有化合物の粒子を導電剤で被覆することによって、粒子間の電子伝導性を確保することができ、集電効率を向上させることができる。その際、請求項４に記載の非水電解液二次電池のように、導電剤として炭素を用いる場合には、正極材料に混合することによって、簡易な被覆が可能となる。さらに、請求項５に記載の非水電解液二次電池のように、導電剤を賦活処理により多孔質化することによって、電子伝導性を確保しつつも、導電剤の被覆によるラフネスファクターの減少によりイオン伝導性が低下することを防止でき、高出力化を図ることができる。   According to the non-aqueous electrolyte secondary battery according to claim 3, by covering the particles of the lithium-containing compound with the conductive agent, the electron conductivity between the particles can be ensured, and the current collection efficiency is improved. be able to. At that time, when carbon is used as the conductive agent as in the non-aqueous electrolyte secondary battery according to claim 4, simple coating is possible by mixing with the positive electrode material. Further, as in the non-aqueous electrolyte secondary battery according to claim 5, by reducing the roughness factor by covering the conductive agent while ensuring electronic conductivity by making the conductive agent porous by activation treatment. Therefore, it is possible to prevent the ion conductivity from being lowered and to increase the output.

以下、本発明に係るリチウムイオン二次電池について、図１を用いて説明する。
本実施形態のリチウムイオン二次電池は、図１に示すように、正極合剤層１１が矩形薄板状の正極集電体１０の表裏面に形成された正極１と、負極合剤層２１が矩形薄板状の負極集電体２０の表裏面に形成された負極２とが、それぞれ板面を対向させて互いの間にセパレータ３を介在させて交互に複数（本実施形態においては4枚ずつ）積層されている。 Hereinafter, a lithium ion secondary battery according to the present invention will be described with reference to FIG.
As shown in FIG. 1, the lithium ion secondary battery of this embodiment includes a positive electrode 1 in which a positive electrode mixture layer 11 is formed on the front and back surfaces of a rectangular thin plate-like positive electrode current collector 10, and a negative electrode mixture layer 21. The negative electrodes 2 formed on the front and back surfaces of the rectangular thin plate-shaped negative electrode current collector 20 are alternately arranged in plural (four in the present embodiment, with the separators 3 interposed therebetween with the plate surfaces facing each other. ) Are stacked.

そして、これらの正極１と負極２とが非水電解液に浸漬されて密閉容器４に収容されており、非水電解液には、正極１および負極２に対して不活性な有機溶媒中にＬｉＢＦ4 、ＬｉＰＦ6 などのリチウム塩を溶解したものが用いられている。 The positive electrode 1 and the negative electrode 2 are immersed in a non-aqueous electrolyte and accommodated in a sealed container 4, and the non-aqueous electrolyte contains an organic solvent inert to the positive electrode 1 and the negative electrode 2. obtained by dissolving a lithium salt such as LiBF 4, LiPF 6 is used.

また、正極１の正極合剤層１１は、ＬｉＦｅ1-xＭxＰＯ4であって、ＭがＬｉ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇ、Ａｌ、Ｔｉ、Ｇａ、Ｃｕ、Ｖ、Ｎｂ、Ｚｒ、Ｃｅ、Ｉｎ、Ｚｎ、ＭｏおよびＹの中から選択される一種以上の元素であり、かつ０＜ｘ≦０．９９のオリビン型構造のリチウム鉄リン酸化合物からなる正極活物質を含有している。この正極活物質は、その平均粒子径が０．１μｍ以上１００μｍ以下であって、その表面が炭素からなる導電剤で被覆されるとともに、この導電剤が賦活処理により多孔質化され、かつ粒子表面積が球体とみなした場合の表面積の２０倍以上１００倍以下となるように調製されている。 The positive electrode mixture layer 11 of the positive electrode 1 is LiFe 1-x M x PO 4 , where M is Li, Ni, Co, Mn, Mg, Al, Ti, Ga, Cu, V, Nb, Zr, It contains one or more elements selected from Ce, In, Zn, Mo and Y, and contains a positive electrode active material made of a lithium iron phosphate compound having an olivine structure of 0 <x ≦ 0.99 . This positive electrode active material has an average particle diameter of 0.1 μm or more and 100 μm or less, and its surface is coated with a conductive agent made of carbon, and the conductive agent is made porous by an activation treatment, and has a particle surface area. Is prepared so as to be 20 times or more and 100 times or less of the surface area when regarded as a sphere.

このような正極活物質は、ＬｉＦｅ1-xＭxＰＯ4のＬｉ源となる化合物、Ｆｅ源となる化合物、Ｍ源となる化合物およびＰＯ4源となる化合物に炭素前駆体を混合して焼成した後に、賦活処理することにより、上記炭素前駆体が賦活処理された炭素の導電剤となって粒子表面に被覆されて得られる。
そして、この正極活物質を導電剤およびバインダーなどと混合してスラリー状にした正極合剤層１１を、正極集電体１０としての金属箔上に塗布し、さらに、この正極集電体１０にタブ１２を取り付けることにより正極１は得られる。 Such a positive electrode active material is obtained by mixing a carbon precursor with a LiFe 1-x M x PO 4 Li source compound, an Fe source compound, an M source compound, and a PO 4 source compound. Thereafter, the carbon precursor is coated on the particle surface by conducting an activation treatment so that the carbon precursor becomes a conductive agent for the activated carbon.
Then, the positive electrode mixture layer 11 in which the positive electrode active material is mixed with a conductive agent and a binder to form a slurry is applied onto a metal foil as the positive electrode current collector 10. The positive electrode 1 is obtained by attaching the tab 12.

また、負極２は、その負極合剤層２１の負極活物質にリチウムイオンを吸蔵放出可能な炭素、好ましくは黒鉛が用いられており、この負極括物質にバインダーなどを加えてスラリー状にした負極合剤層２１を負極集電体２０としての金属箔に塗布し、さらに、この負極集電体２０にタブ２２を取り付けることにより得られる。   In the negative electrode 2, carbon capable of occluding and releasing lithium ions, preferably graphite, is used for the negative electrode active material of the negative electrode mixture layer 21. A negative electrode obtained by adding a binder or the like to this negative electrode bulk material to form a slurry. The mixture layer 21 is obtained by coating a metal foil as the negative electrode current collector 20 and attaching a tab 22 to the negative electrode current collector 20.

そして、上述の複数枚の正極１と負極２とを、正極１のタブ１２と負極２のタブ２２とが対向辺の一方側と他方側とに交互に配置されるように交互に積層して、アルミラミネートフィルムからなる袋状の外装体に挿入するとともに、この外装体内に非水電解液を注入した後に、この外装体の開口部を封止することによって密閉容器４が形成されて、正極１と負極２とが非水電解液に浸漬されて密閉容器４に収容されたリチウムイオン二次電池が組み立てられる。   Then, the plurality of positive electrodes 1 and negative electrodes 2 described above are alternately stacked such that the tabs 12 of the positive electrode 1 and the tabs 22 of the negative electrode 2 are alternately arranged on one side and the other side of the opposite side. The sealed container 4 is formed by inserting the non-aqueous electrolyte into the outer package and then sealing the opening of the outer package after being inserted into the bag-shaped outer package made of an aluminum laminate film. 1 and the negative electrode 2 are immersed in the nonaqueous electrolyte solution, and the lithium ion secondary battery accommodated in the airtight container 4 is assembled.

以上のように構成されるリチウムイオン二次電池は、その正極活物質として、ＬｉＦｅＰＯ4のＦｅの一部を置換して、ＬｉＦｅ1-xＭxＰＯ4のＭがＬｉ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇ、Ａｌ、Ｔｉ、Ｇａ、Ｃｕ、Ｖ、Ｎｂ、Ｚｒ、Ｃｅ、Ｉｎ、Ｚｎ、ＭｏおよびＹの中から選択される一種以上の元素である０＜ｘ≦０．９９のオリビン型構造のリチウム鉄リン酸化合物を用いたため、リチウム鉄リン酸化合物粒子内のイオン伝導性を著しく向上させることができる。 The lithium ion secondary battery configured as described above replaces part of Fe of LiFePO 4 as the positive electrode active material, and M of LiFe 1-x M x PO 4 is Li, Ni, Co, Mn Mg, Al, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Zn, Mo, and Y are one or more elements selected from olivine type structures of 0 <x ≦ 0.99 Since the lithium iron phosphate compound is used, the ionic conductivity in the lithium iron phosphate compound particles can be remarkably improved.

また、リチウム鉄リン酸化合物の平均粒子径を０．１〜１００μｍとしたため、上述のリチウムイオン二次電池を作製する際の凝集の発生を抑制して、安定したスラリー調製を行うことができる。これに加えて、ラフネスファクターを２０倍以上１００倍以下としたため、上述の粒子内のイオン伝導性を一段と向上させることができ、微粒子化しなくとも、リチウム含有化合物の粒子内部まで電池反応を行わせることが可能となる。   Moreover, since the average particle diameter of the lithium iron phosphate compound is 0.1 to 100 μm, it is possible to suppress the occurrence of aggregation when the above-described lithium ion secondary battery is manufactured, and to perform stable slurry preparation. In addition, since the roughness factor is 20 times or more and 100 times or less, the ionic conductivity in the above-mentioned particles can be further improved, and the battery reaction can be carried out to the inside of the lithium-containing compound particles without making the particles fine. It becomes possible.

さらには、 リチウム含有化合物の粒子を導電剤で被覆することによって、粒子間の電子伝導性を確保することができ、延いては集電体などのリチウムイオン二次電池の構成部品などとの電子伝導性も確保でき、集電効率を向上させることができる。   Furthermore, by covering the particles of the lithium-containing compound with a conductive agent, the electron conductivity between the particles can be secured, and as a result, the electrons with the components of the lithium ion secondary battery such as a current collector can be secured. Conductivity can also be secured and current collection efficiency can be improved.

その際、導電剤として炭素を用いる場合には、ＬｉＦｅ1-xＭxＰＯ4のＬｉ源となる化合物、Ｆｅ源となる化合物、Ｍ源となる化合物およびＰＯ4源となる化合物に炭素前駆体を混合して焼成することにより、上記炭素前駆体を炭素導電剤としてリチウム含有化合物の粒子表面に被覆でき、よって、正極活物質の材料化合物に混合することによって、簡易な被覆が可能となる。 In this case, when carbon is used as the conductive agent, a carbon precursor is added to the LiFe 1-x M x PO 4 Li source compound, the Fe source compound, the M source compound, and the PO 4 source compound. By mixing and firing, the carbon precursor can be coated on the particle surface of the lithium-containing compound as a carbon conductive agent, and therefore, simple coating is possible by mixing with the material compound of the positive electrode active material.

さらに、上記焼成後に賦活処理することにより、上記炭素前駆体を賦活処理された炭素導電剤としてリチウム含有化合物の粒子表面に被覆できる。すると、導電剤が賦活処理により多孔質化されているため、電子伝導性を確保しつつも、導電剤の被覆によるラフネスファクターの減少によりイオン伝導性が低下することを防止でき、さらなるリチウムイオン二次電池の高出力化を図ることができる。   Furthermore, by performing the activation treatment after the firing, the carbon precursor can be coated on the particle surface of the lithium-containing compound as a carbon conductive agent subjected to the activation treatment. Then, since the conductive agent is made porous by the activation treatment, it is possible to prevent the ionic conductivity from being lowered due to the decrease in the roughness factor due to the coating of the conductive agent while ensuring the electronic conductivity. The output of the secondary battery can be increased.

実施例として、正極活物質であるＬｉＦｅ1-xＭxＰＯ4のＭにＮｉ、Ｃｏ、Ｍｎ、Ｍｇ、Ａｌ、Ｔｉ、Ｇａ、Ｃｕ、Ｖ、Ｎｂ、Ｚｒ、Ｃｅ、Ｉｎ、ＭｏまたはＹを選択した表１に示す実施例１〜１５の正極１などを以下の方法で作製することにより組み立てたリチウムイオン二次電池の性能試験を行った。 As an example, Ni, Co, Mn, Mg, Al, Ti, Ga, Cu, V, Nb, Zr, Ce, In, Mo, or Y is added to M of the positive electrode active material LiFe 1-x M x PO 4. The performance test of the lithium ion secondary battery assembled by producing the positive electrode 1 etc. of Examples 1-15 shown in the selected Table 1 by the following method was performed.

（正極活物質の調製）
鉄源としてシュウ酸鉄二水和物（ＦｅＣ2Ｏ4・2Ｈ2Ｏ）、この鉄源のＦｅを上記Ｍに置換する置換金属源として金属シュウ酸水和物（ＭＣ2Ｏ4Ｈ2Ｏ）、リン酸源としてリン酸二水素アンモニウム（ＮＨ4 Ｈ2ＰＯ4）およびリチウム源として炭酸リチウム（Ｌｉ2ＣＯ3）を、ＬｉＦｅ0.5Ｍ0.5ＰＯ4を合成するための所定のモル比に計量し、これにショ糖を混合した。
その際、上記金属シュウ酸水和物として、実施例１の正極活物質ではＭがＮｉであるため、ニッケルシュウ酸水和物（ＮｉＣ2Ｏ4・yＨ2Ｏ）を、同様に、実施例２ではコバルトシュウ酸水和物（ＣｏＣ2Ｏ4・yＨ2Ｏ）を、実施例３ではマンガンシュウ酸水和物（ＭｎＣ2Ｏ4・yＨ2Ｏ）を、実施例４ではマグネシウムシュウ酸水和物（ＭｇＣ2Ｏ4・yＨ2Ｏ）を、実施例５ではアルミニウムシュウ酸水和物（Ａｌ2（Ｃ2Ｏ4）3・yＨ2Ｏ）を、実施例６ではチタンシュウ酸水和物（Ｔｉ2（Ｃ2Ｏ4）3・yＨ2Ｏ）を、実施例７ではガリウムシュウ酸水和物（Ｇａ2（Ｃ2Ｏ4）3・yＨ2Ｏ）を、実施例８では銅シュウ酸水和物（Ｃｕ2Ｃ2Ｏ4・yＨ2Ｏ）を、実施例９ではバナジウムシュウ酸水和物（Ｖ2（Ｃ2Ｏ4）3・yＨ2Ｏ）を、実施例１０ではニオブシュウ酸水和物（Ｎｂ2（Ｃ2Ｏ4）3・yＨ2Ｏ）を、実施例１１ではジルコニウムシュウ酸水和物（ＺｒＣ2Ｏ4・yＨ2Ｏ）を、実施例１２ではセリウムシュウ酸水和物（Ｃｅ2（Ｃ2Ｏ4）3・yＨ2Ｏ）を、実施例１３ではインジウムシュウ酸水和物（Ｉｎ2（Ｃ2Ｏ4）3・yＨ2Ｏ）を、実施例１４ではモリブデンシュウ酸水和物（ＭｏＯ（Ｃ2Ｏ4）2・yＨ2Ｏ）を、実施例１５ではイットリウムシュウ酸水和物（Ｙ2（Ｃ2Ｏ4）3・yＨ2Ｏ）それぞれ用いた。 (Preparation of positive electrode active material)
Iron oxalate dihydrate (FeC 2 O 4 .2H 2 O) as an iron source, and metal oxalate hydrate (MC 2 O 4 H 2 O) as a substitution metal source for substituting Fe of this iron source with M , Ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ) as a phosphoric acid source and lithium carbonate (Li 2 CO 3 ) as a lithium source were weighed to a predetermined molar ratio for synthesizing LiFe 0.5 M 0.5 PO 4. This was mixed with sucrose.
At that time, since M is Ni in the positive electrode active material of Example 1 as the metal oxalic acid hydrate, nickel oxalic acid hydrate (NiC 2 O 4 .yH 2 O) is similarly used in the example. In Example 2, cobalt oxalic acid hydrate (CoC 2 O 4 .yH 2 O) is used. In Example 3, manganese oxalic acid hydrate (MnC 2 O 4 .yH 2 O) is used. In Example 4, magnesium oxalic acid water is used. Japanese hydrate (MgC 2 O 4 · yH 2 O), aluminum oxalic acid hydrate (Al 2 (C 2 O 4 ) 3 · yH 2 O) in Example 5, and titanium oxalic acid hydrate in Example 6 (Ti 2 (C 2 O 4 ) 3 .yH 2 O), gallium oxalate hydrate (Ga 2 (C 2 O 4 ) 3 .yH 2 O) in Example 7, and copper in Example 8 oxalic acid hydrate (Cu 2 C 2 O 4 · yH 2 O) a, example 9, vanadium oxalate hydrate (V 2 (C 2 O 4 ) 3 · yH 2 O) The Niobushuu acid hydrate in Example 10 (Nb 2 (C 2 O 4) 3 · yH 2 O), Example 11, zirconium oxalate hydrate (ZrC 2 O 4 · yH 2 O), performed In Example 12, cerium oxalic acid hydrate (Ce 2 (C 2 O 4 ) 3 .yH 2 O) was used. In Example 13, indium oxalic acid hydrate (In 2 (C 2 O 4 ) 3 .yH 2 O) was used. ), Molybdenum oxalate hydrate (MoO (C 2 O 4 ) 2 .yH 2 O) in Example 14, and yttrium oxalate hydrate (Y 2 (C 2 O 4 ) 3. yH 2 O) was used respectively.

次いで、上記混合物に２−プロパノールを溶媒として加えたものを、ボールミルで１０時間粉砕混合した後に真空乾燥させて２−プロパノールを除去することにより、実施例１〜１５の正極活物質の前駆体を得た。
これら実施例１〜１５の各前駆体を、それぞれアルミナ製の香鉢に入れ、焼成炉にて０．５Ｌ／分のアルゴン流通下で３００℃、５時間の仮焼成後に、そのまま温度のみを昇温させて６５０℃で２０時間焼成することにより、Ｆｅ0.5Ｍ0.5ＰＯ4の粉末を合成した。さらに、この合成粉末を賦活炉にて７５０℃の水蒸気下で多孔質化することにより実施例１〜１５の正極活物質を作製して、これらの正極活物質の平均粒径を計測して表１に示し、かつ比表面積として単位重量に含まれる全粒子の表面積（ｍ2／ｇ）を計測するとともにラフネスファクターを求めて、それぞれ表１に示した。 Subsequently, what added 2-propanol as a solvent to the said mixture was pulverized and mixed for 10 hours with a ball mill, and then vacuum-dried to remove 2-propanol, whereby the positive electrode active material precursors of Examples 1 to 15 were obtained. Obtained.
Each of the precursors of Examples 1 to 15 was placed in an alumina incense bowl, and after calcining at 300 ° C. for 5 hours under an argon flow of 0.5 L / min in a firing furnace, only the temperature was increased. The powder of Fe 0.5 M 0.5 PO 4 was synthesized by heating and baking at 650 ° C. for 20 hours. Further, this synthetic powder was made porous under steam at 750 ° C. in an activation furnace to produce positive electrode active materials of Examples 1 to 15, and the average particle diameter of these positive electrode active materials was measured and displayed. The surface area (m 2 / g) of all particles contained in the unit weight was measured as a specific surface area, and the roughness factor was determined and shown in Table 1, respectively.

（正極１の作製）
次に、上記実施例１〜１５の各正極活物質に、それぞれ導電剤としてのアセチレンブラックおよびバインダーとしてのポリフッ化ビニリデンを混合し、さらに、この混合物にＮメチルピロリドンを加えてスラリー状にして実施例１〜１５の正極スラリーを合成した。その際、正極活物質と導電剤とバインダーとが質量比で９０：５：５となるように調製した。 (Preparation of positive electrode 1)
Next, acetylene black as a conductive agent and polyvinylidene fluoride as a binder were mixed with each of the positive electrode active materials of Examples 1 to 15, and N methylpyrrolidone was added to the mixture to form a slurry. The positive electrode slurries of Examples 1-15 were synthesized. At that time, the positive electrode active material, the conductive agent, and the binder were prepared in a mass ratio of 90: 5: 5.

次いで、実施例１〜１５の各正極スラリーを、それぞれ正極集電体１０としてのアルミニウム箔上に塗布して乾燥させた後に圧延ローラを用いて圧延して、さらに、上記アルミニウム箔にタブ１２を取り付けることにより、正極合剤層１１が形成された実施例１〜１５の正極１を作製した。   Next, each of the positive electrode slurries of Examples 1 to 15 was applied on an aluminum foil as the positive electrode current collector 10 and dried, and then rolled using a rolling roller. Further, the tab 12 was formed on the aluminum foil. By attaching, the positive electrode 1 of Examples 1-15 in which the positive electrode mixture layer 11 was formed was produced.

（負極２の作製）
負極活物質としての黒鉛と、バインダーとしてのポリフッ化ビニリデンとを混合して、さらに、これらの混合物に増粘剤としてのＮメチルピロリドンを加えることにより、負極スラリーを合成した。その際、負極活物質とバインダーと増粘剤とが質量比で９５：３：２となるように調製した。 (Preparation of negative electrode 2)
A negative electrode slurry was synthesized by mixing graphite as a negative electrode active material and polyvinylidene fluoride as a binder, and further adding N-methylpyrrolidone as a thickener to these mixtures. At that time, the negative electrode active material, the binder, and the thickener were prepared so as to have a mass ratio of 95: 3: 2.

次いで、この負極スラリーを、負極集電体２０としての銅箔上に塗布して乾燥させた後に圧延ローラを用いて圧延して、さらに、上記銅箔にタブ２２を取り付けることにより、負極合剤層２１が形成された負極２を作製した。   Next, the negative electrode slurry is applied onto a copper foil as the negative electrode current collector 20 and dried, and then rolled using a rolling roller, and a tab 22 is attached to the copper foil, whereby a negative electrode mixture is obtained. The negative electrode 2 in which the layer 21 was formed was produced.

（電解液の調製）
エチレンカーボネートとエチルメチルカーボネートとを体積比３：７で混合した溶媒に、１モル／ＬのＬｉＰＦ6を溶解させ、さらに、ビニレンカーボネートを加えて電解液を調製した。 (Preparation of electrolyte)
1 mol / L LiPF 6 was dissolved in a solvent in which ethylene carbonate and ethyl methyl carbonate were mixed at a volume ratio of 3: 7, and vinylene carbonate was further added to prepare an electrolytic solution.

（電池の組み立て）
まず、正極１と負極２とを、上述の最良の実施形態と同様に板面が対向して互いの間にセパレータ３が介在するように交互に積層して電極体を構成した。なお、実施例１〜１５について、各電極体は正極１と負極２とが同一枚数となるように構成されている。
次いで、この電極体を、真空中にて１０５℃で２０時間乾燥させた後にアルゴン雰囲気下のグローブボックス内にて、厚み０．１１ｍｍのアルミラミネートフィルムを袋状に形成した外装体に挿入し、その後、この外装体内に上記電解液を注入して、外装体の開口を封止して実施例１〜１５のリチウムイオン二次電池を組み立てた。
従って、これらの実施例１〜１５のリチウムイオン二次電池は、正極活物質以外は同一の構成を有している。 (Battery assembly)
First, the positive electrode 1 and the negative electrode 2 were laminated | stacked alternately so that the plate | board surface might oppose and the separator 3 might interpose each other like the above-mentioned best embodiment, and the electrode body was comprised. In addition, about Examples 1-15, each electrode body is comprised so that the positive electrode 1 and the negative electrode 2 may become the same number.
Next, after this electrode body was dried in vacuum at 105 ° C. for 20 hours, it was inserted into an outer package formed of a 0.11 mm thick aluminum laminate film in a bag shape in a glove box under an argon atmosphere, Then, the said electrolyte solution was inject | poured in this exterior body, the opening of the exterior body was sealed, and the lithium ion secondary battery of Examples 1-15 was assembled.
Therefore, the lithium ion secondary batteries of Examples 1 to 15 have the same configuration except for the positive electrode active material.

（比較例／リチウムイオン二次電池の作製）
次いで、上述の実施例において正極活物質の調製の際に、上記置換金属源としての金属シュウ酸水和物（ＭＣ2Ｏ4Ｈ2Ｏ）と炭素前駆体とを混合しなかったこと以外は、実施例１〜１５と同様にして正極活物質を調製することにより作製した正極１と、実施例１〜１５と同一の負極２および電解液とを用いて、比較例のリチウムイオン二次電池を組み立てた。 (Comparative Example / Production of Lithium Ion Secondary Battery)
Next, in preparing the positive electrode active material in the above examples, except that the metal oxalic acid hydrate (MC 2 O 4 H 2 O) as the substitution metal source was not mixed with the carbon precursor. A lithium ion secondary battery of a comparative example using the positive electrode 1 produced by preparing a positive electrode active material in the same manner as in Examples 1 to 15 and the same negative electrode 2 and electrolyte as in Examples 1 to 15 Assembled.

（性能試験）
次いで、上述の実施例１〜１５および比較例のリチウムイオン二次電池について、インピーダンス、初期放電容量、出力特性およびサイクル特性を以下の方法にて計測して、それぞれ表１に示した。 (performance test)
Next, for the lithium ion secondary batteries of Examples 1 to 15 and the comparative example, impedance, initial discharge capacity, output characteristics, and cycle characteristics were measured by the following methods, and are shown in Table 1, respectively.

（インピーダンス）
実施例１〜１５および比較例のリチウムイオン二次電池について、それぞれ直流電流抵抗値（ＤＣＲ）を計測して、比較例のリチウムイオン二次電池のＤＣＲを１００とした際の相対値を表1に示した。 (Impedance)
For the lithium ion secondary batteries of Examples 1 to 15 and the comparative example, the direct current resistance value (DCR) was measured, and the relative values when the DCR of the lithium ion secondary battery of the comparative example was set to 100 are shown in Table 1. It was shown to.

（初期放電容量）
実施例１〜１５および比較例のリチウムイオン二次電池について、正極１の単位面積あたりの電流密度０．５ｍＡ／ｃｍ2にて、25℃の温度条件の下、３〜４Ｖの作動電圧範囲で充放電試験を行って初期放電容量を測定し、ＬｉＦｅＰＯ4の理論放電容量である１７０ｍＡｈ／ｇを１００とした場合の放電容量の比率を表１に示した。 (Initial discharge capacity)
For the lithium ion secondary batteries of Examples 1 to 15 and the comparative example, the current density per unit area of the positive electrode 1 was 0.5 mA / cm 2 and the operating voltage range was 3 to 4 V under the temperature condition of 25 ° C. The charge / discharge test was performed to measure the initial discharge capacity. Table 1 shows the ratio of the discharge capacity when the theoretical discharge capacity of LiFePO 4 is 170 mAh / g.

（出力特性）
実施例１〜１５および比較例のリチウムイオン二次電池について、上述のように初期放電容量を測定した後に、そのまま正極１の単位面積あたりの電流密度を５ｍＡに上昇させて同様に放電容量を測定し、上記初期放電容量を１００とした場合の電流密度５ｍＡで測定した放電容量の比率を求めて表１に示した。 (Output characteristics)
For the lithium ion secondary batteries of Examples 1 to 15 and the comparative example, after measuring the initial discharge capacity as described above, the current density per unit area of the positive electrode 1 was increased to 5 mA and the discharge capacity was measured in the same manner. The ratio of the discharge capacity measured at a current density of 5 mA when the initial discharge capacity was 100 was determined and shown in Table 1.

（サイクル特性）
実施例１〜１５および比較例のリチウムイオン二次電池について、それぞれ０．５ｍＡ／ｃｍ2の電流密度にて２５℃の温度条件の下、３．０Ｖ〜４．０Ｖの作動電圧範囲での繰り返しの充放電を行うサイクル試験を行った後の初期容量に対する１０００サイクル後の容量維持率を表１に示した。 (Cycle characteristics)
About the lithium ion secondary battery of Examples 1-15 and a comparative example, it repeats in the operating voltage range of 3.0V-4.0V under the temperature conditions of 25 degreeC at the current density of 0.5 mA / cm < 2 >, respectively. Table 1 shows the capacity retention ratio after 1000 cycles with respect to the initial capacity after performing a cycle test for charging and discharging.

Figure 2010086657
Figure 2010086657

表１から判るように、比較例のリチウムイオン二次電池と比較して実施例１〜１５のリチウムイオン二次電池は、いずれもインピーダンスが小さく、初期放電容量が大きく、出力特性およびサイクル特性にも優れている。   As can be seen from Table 1, compared with the lithium ion secondary battery of the comparative example, each of the lithium ion secondary batteries of Examples 1 to 15 has a small impedance, a large initial discharge capacity, an output characteristic and a cycle characteristic. Is also excellent.

本実施形態のリチウムイオン二次電池を示す外観斜視図である。It is an external appearance perspective view which shows the lithium ion secondary battery of this embodiment. 図１のリチウムイオン二次電池における正極１と負極２の積層構造を示す断面図である。FIG. 2 is a cross-sectional view showing a laminated structure of a positive electrode 1 and a negative electrode 2 in the lithium ion secondary battery of FIG. 図２のＩＩＩ−ＩＩＩ線矢示図である。FIG. 3 is a view taken along line III-III in FIG. 2.

符号の説明Explanation of symbols

１ 正極
２ 負極
３ セパレータ
４ 密閉容器
１０ 正極集電体
１１ 正極合剤層
１２ 正極のタブ
２０ 負極集電体
２１ 負極合剤層
２２ 負極のタブ DESCRIPTION OF SYMBOLS 1 Positive electrode 2 Negative electrode 3 Separator 4 Sealed container 10 Positive electrode collector 11 Positive electrode mixture layer 12 Positive electrode tab 20 Negative electrode collector 21 Negative electrode mixture layer 22 Negative electrode tab

Claims (5)

負極と、リチウム含有化合物を備えた正極とが非水電解液に浸漬されてなる非水電解液二次電池において、
前記正極のリチウム含有化合物は、ＬｉＦｅ1-xＭxＰＯ4であって、ＭがＬｉ、Ｎｉ、Ｃｏ、Ｍｎ、Ｍｇ、Ａｌ、Ｔｉ、Ｇａ、Ｃｕ、Ｖ、Ｎｂ、Ｚｒ、Ｃｅ、Ｉｎ、Ｚｎ、ＭｏおよびＹの中から選択される一種以上の元素であり、かつ０＜ｘ≦０．９９のオリビン型構造のリチウム鉄リン酸化合物からなることを特徴とする非水電解液二次電池。 In a non-aqueous electrolyte secondary battery in which a negative electrode and a positive electrode provided with a lithium-containing compound are immersed in a non-aqueous electrolyte,
The lithium-containing compound of the positive electrode is LiFe 1-x M x PO 4 , where M is Li, Ni, Co, Mn, Mg, Al, Ti, Ga, Cu, V, Nb, Zr, Ce, In, A non-aqueous electrolyte secondary battery comprising one or more elements selected from Zn, Mo and Y and comprising a lithium iron phosphate compound having an olivine structure of 0 <x ≦ 0.99 . 前記正極のリチウム含有化合物は、その平均粒子径が０．１μｍ以上１００μｍ以下であり、かつ粒子表面積が球体とみなした場合の表面積の２０倍以上１００倍以下であることを特徴とする請求項１に記載の非水電解液二次電池。   The lithium-containing compound of the positive electrode has an average particle size of 0.1 μm or more and 100 μm or less, and a particle surface area of 20 times or more and 100 times or less of a surface area when regarded as a sphere. A nonaqueous electrolyte secondary battery according to 1. 前記正極のリチウム含有化合物は、その表面が導電剤で被覆されていることを特徴とする請求項１または２に記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to claim 1, wherein a surface of the lithium-containing compound of the positive electrode is coated with a conductive agent. 前記導電剤は、炭素であることを特徴とする請求項３に記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to claim 3, wherein the conductive agent is carbon. 前記導電剤は 賦活処理により多孔質化されていることを特徴とする請求項３または４に記載の非水電解液二次電池。   The non-aqueous electrolyte secondary battery according to claim 3 or 4, wherein the conductive agent is made porous by an activation treatment.
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Cited By (7)

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JP2013514606A (en) * 2009-12-17 2013-04-25 フォステック リチウム インコーポレイテッド Method for improving electrochemical performance of alkali metal oxyanion electrode material, and alkali metal oxyanion electrode material obtained thereby
JP2013518023A (en) * 2010-01-28 2013-05-20 ズード−ケミー アーゲー Substituted lithium metal phosphate
JP2013533837A (en) * 2010-05-21 2013-08-29 ビーエーエスエフ ソシエタス・ヨーロピア Compounds for the production of electrochemical cells and their use
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JP2014082219A (en) * 2014-01-30 2014-05-08 Sumitomo Metal Mining Co Ltd Positive electrode active material for lithium secondary batteries and manufacturing method thereof, and lithium secondary battery arranged by use of such positive electrode active material
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013514606A (en) * 2009-12-17 2013-04-25 フォステック リチウム インコーポレイテッド Method for improving electrochemical performance of alkali metal oxyanion electrode material, and alkali metal oxyanion electrode material obtained thereby
JP2013518023A (en) * 2010-01-28 2013-05-20 ズード−ケミー アーゲー Substituted lithium metal phosphate
JP2013533837A (en) * 2010-05-21 2013-08-29 ビーエーエスエフ ソシエタス・ヨーロピア Compounds for the production of electrochemical cells and their use
JP2013247109A (en) * 2012-05-23 2013-12-09 Samsung Sdi Co Ltd Positive electrode active material and lithium secondary battery
US9979023B2 (en) 2012-05-23 2018-05-22 Samsung Sdi Co., Ltd. Positive active material and rechargeable lithium battery including same
JP2014082219A (en) * 2014-01-30 2014-05-08 Sumitomo Metal Mining Co Ltd Positive electrode active material for lithium secondary batteries and manufacturing method thereof, and lithium secondary battery arranged by use of such positive electrode active material
JP6288342B1 (en) * 2017-03-30 2018-03-07 住友大阪セメント株式会社 Positive electrode material for lithium ion secondary battery and lithium ion secondary battery
JP2018170187A (en) * 2017-03-30 2018-11-01 住友大阪セメント株式会社 Positive electrode material for lithium ion secondary battery and lithium ion secondary battery
CN113346125A (en) * 2021-05-31 2021-09-03 廖福宁 Lithium ion battery

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